Oxidative cross-coupling has proved to be one of the most straightforward strategies for forming carbon-carbon and carbon-heteroatom bonds from easily available precursors. Over the past two decades, tremendous efforts have been devoted in this field and significant advances have been achieved. However, in order to remove the surplus electrons from substrates for chemical bonds formation, stoichiometric oxidants are usually needed. Along with the development of modern sustainable chemistry, considerable efforts have been devoted to perform the oxidative cross-coupling reactions under external-oxidant-free conditions. Electrochemical synthesis is a powerful and environmentally benign approach, which can not only achieve the oxidative cross-couplings under external-oxidant-free conditions, but also release valuable hydrogen gas during the chemical bond formation. Recently, the electrochemical oxidative cross-coupling with hydrogen evolution reactions has been significantly explored. This Account presents our recent efforts toward the development of electrochemical oxidative cross-coupling with hydrogen evolution reactions. (1) We explored the oxidative cross-coupling of thiols/thiophenols with arenes, heteroarenes, and alkenes for C-S bond formation. (2) Using the strategy of electrochemical oxidative C-H/N-H cross-coupling with hydrogen evolution, we successfully realized the C-H amination of phenols, anilines, imidazopyridines, and even ethers. (3) Employing halide salts as the green halogenating reagents, we developed a clean C-H halogenation protocol under electrochemical oxidation conditions. To address the limitation that this reaction had to carry out in aqueous solvent, we also developed an alternative method that uses CBr₄, CHBr₃, CH₂Br₂, CCl₃Br, and CCl₄ as halogenating reagents and the mixture of acetonitrile and methanol as cosolvent. (4) We also developed an approach for constructing C-O bonds in a well-developed electrochemical oxidative cross-coupling with hydrogen evolution manner. (5) Under mild external-oxidant-free electrochemical conditions, we realized the C(sp²)-H and C(sp³)-H phosphonylation with modest to high yields. (6) We successfully achieved the S-H/S-H cross-coupling with hydrogen evolution under electrochemical oxidation conditions. By anodic oxidation instead of chemical oxidants, the overoxidation of thiols and thiophenols was well avoided. (7) The methods for constructing structurally diverse heterocyclic compounds were also developed via the electrochemical oxidative annulations. (8) We have also applied the electrochemical oxidative cross-coupling with hydrogen evolution strategy to the alkenes difunctionalization for constructing multiple bonds in one step, such as C-S/C-O bonds, C-S/C-N bonds, C-Se/C-O bonds, and C-Se/C-N bonds. We hope our studies will stimulate the research interest of chemists and pave the way for the discovery of more electrochemical oxidative cross-coupling with hydrogen evolution reactions.

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